The pair – who worked alongside one another when the Portuguese was in charge of Inter – spoke in the aftermath of Real Madrid’s 1-1 draw with Manchester City.
Mourinho and Benitez had a stormy relationship when the Blancos boss was at Chelsea and the Spaniard in charge of Liverpool.
And after Wednesday’s Champions League encounter Mourinho was informed of the breaking news at Stamford Bridge and shared a joke with Maicon regarding the move.
“Your friend Benitez is going to Chelsea,” the Brazilian said to Mourinho, according to La Sexta.
The 49-year-old responded: “The fat one? Well then Materazzi should be his assistant.”
Materazzi had previously revealed how Benitez made him tear down newspaper cuttings from his locker of victories with Mourinho and Marcello Lippi when The Blues’ interim coach joined Inter in 2010.